Branched polyesters prepared from macrocyclic poly(Alkylene Dicarboxylate) oligomers

ABSTRACT

Cyclic tin catalysts are employed for the preparation of branched polyesters from macrocyclic polyester oligomers. They are less susceptible than previously known catalysts to the presence of acidic impurities in the oligomer compositions.

BACKGROUND OF THE INVENTION

This invention relates to the polymerization of macrocyclic polyester oligomer compositions. More particularly, it relates to an improved method for such polymerization which is capable of producing novel branched polyesters.

The preparation of macrocyclic poly(alkylene dicarboxylate) oligomers and their polymerization to linear polyesters is described in U.S. Pat. Nos. 5,039,783, 5,214,158 and 5,231,161 and in copending, commonly owned applications Ser. Nos. 07/702,577 and 07/978,583. The catalysts employed for such polymerization include various organotin compounds and titanate esters.

Polymerization using these Catalysts is quite successful and affords polyesters having excellent properties and a wide variety of potential applications. However, the catalysts are somewhat sensitive to impurities present in the macrocyclic polyesters, particularly acidic impurities which can include water, hydroxy compounds and carboxylic acids and their anhydrides.

In the presence of such impurities, the catalyst may be partially deactivated and polymerization may be incomplete or may yield polymers with low weight average molecular weights. Attempts to increase polymer yield by increasing the proportion of catalyst in the polymerization mixture cause significant further reductions in the molecular weight of the linear polymer, since the catalyst becomes part of the polymer end group and increased amounts of catalyst compete for the same proportions of structural units in the macrocyclic oligomers.

Another problem sometimes encountered with linear polyesters prepared from macrocyclic oligomers, particularly when employed in fiber-reinforced composites, is a tendency to flow or "creep" under high load. This property is detrimental to the use of such polyesters under high load conditions, such as for the fabrication of automobile frames which must carry large weights and be extremely rigid and dimensionally stable.

It would be desirable, therefore, to develop improved catalysts with high activity for the polymerization of macrocyclic oligomers containing increased proportions of impurities, especially acidic impurities. It would be further desirable to convert macrocyclic oligomer compositions to branched polyesters having improved dimensional stability, for use as load-bearing members in automobiles and the like.

SUMMARY OF INVENTION

The present invention provides a novel class of branched polyesters with high dimensional stability which may be produced from macrocyclic oligomers. Said oligomers and polyesters may be employed in the fabrication of fiber-reinforced composites and the like.

The invention includes branched poly(alkylene dicarboxylates) having the formula ##STR1## wherein R¹ is an alkylene or mono- or polyoxyalkylene radical containing a straight chain of about 2-8 atoms, R² is a C₁₋₄ primary alkyl radical, A is a m- or p-linked monocyclic aromatic or alicyclic radical, X is a linear or branched organic end group, y has an average value of at least about 10 and m is 0 or 1.

DETAILED DESCRIPTION; PREFERRED EMBODIMENTS

In formula I, the R² radicals may be methyl, ethyl, n-propyl or n-butyl and are preferably methyl or ethyl. The X radicals are organic end groups and may themselves be polymeric. For example, they may have structures similar to the portion of formula I to the left of the tin atom, bound through oxygen to additional tin atoms. The precise nature of the end groups will be apparent to those skilled in the art but is not critical for the purposes of the invention.

The branched polyesters of this invention may be prepared from macrocyclic polyester oligomers comprising structural units of the formula ##STR2## wherein R¹ and A are as previously defined. Said macrocyclic polyester oligomers may themselves be prepared by contacting at least one diol of the formula HO-R¹ -OH and at least one diacid chloride of the formula ##STR3## under substantially anhydrous conditions and in the presence of a substantially water-immiscible organic solvent, with at least one unhindered tertiary amine; said contact being conducted at a temperature from about -25° to about +25° C. This procedure is described in detail in the aforementioned patents and applications, and it is therefore deemed unnecessary to provide a detailed explanation herein. In most instances, the products are mixtures of macrocyclic oligomers having differing degrees of polymerization.

To prepare the branched polyesters, the macrocyclic polyester oligomers are contacted with a macrocyclic polyester oligomer polymerization catalyst having the formula ##STR4## wherein each R³ is a C₁₋₁₀ alkyl radical, preferably a primary radical such as methyl, ethyl, n-butyl, n-hexyl, n-octyl, 2-ethylhexyl or n-decyl, and most preferably a C₃₋₁₀ radical, and Z is ##STR5##

The Z value may be a single carbon atom or a tetravalent radical of formula IV. The catalysts wherein Z is a single carbon atom are known compounds, being disclosed, for example, in U.S. Pat. No. 3,969,319 and in Lin et al., ACS Polymer Preprints, 33 (1), 1111-1112 (1993). Their use affords branched polyesters having formula I in which m is 0.

The catalysts in which Z has formula IV are novel trisstannoxanes; they are disclosed and claimed in copending, commonly owned application Ser. No. 08/262,793. They afford branched polyesters in which m is 1. Said novel trisstannoxanes may be prepared by the reaction of a dialkyltin oxide of the formula (R³)₂ SnO with a triol of the formula R² (CH₂ OH)₃, such as 1,1,1-tris(hydroxymethyl)ethane or 1,1,1-tris(hydroxymethyl)propane, in a molar ratio of at least about 1.2:1 and preferably about 1.25-1.75:1. The reaction is preferably conducted in solution in a substantially non-polar solvent such as toluene and at a temperature in the range of about 100°-150° C. An inert atmosphere such as nitrogen is usually employed and water is removed as it is formed, preferably as an azeotropic mixture with the solvent employed.

The preparation of the novel catalysts is illustrated by the following example.

Example 1

A mixture of 2.68 grams (20 mmol.) of 1,1,1-tris(hydroxymethyl)propane, 10.83 grams (30 mmol.) of dioctyltin(IV) oxide and 25 mi. of toluene was heated under reflux in a nitrogen atmosphere in a 3-necked flask equipped with a Dean-Stark trap, with removal of water as an azeotropic mixture with toluene. After refluxing for 1 hour, the trap was replaced with another trap filled with 3A molecular sieves and refluxing was continued for 4 hours. The resulting solution was filtered under nitrogen while hot and the solvent was removed by distillation. The residue was dried under vacuum at 100° C. Upon cooling, the desired bis[(5-ethyl-2,2-dioctyl-2-stanna-1,3-dioxacyclohexane )-5-methyleneoxy]dioctyltin in impure form solidified to a waxy solid having a melting point of 78°-83° C. The crude yield was 12.5 grams (96.3% of theoretical). A portion of the product, upon recrystallization from hexane, melted at 91°-93° C.

The macrocyclic polyester oligomers are converted to the branched polyesters of this invention by contact with said catalyst at a temperature in the range of about 160°-300° C., preferably 160°-250° C. The latter is typically employed in the amount of about 0.01-2.0 and preferably about 0.05-1.0 mole percent based on structural units in the oligomers. This method of polymerizing macrocyclic polyester oligomers is disclosed and claimed in copending, commonly owned application Ser. No. 08/262,795.

The branched polyesters of this invention have advantageous properties in addition to their branched structure. For example, they have high molecular weights even when prepared from oligomer mixtures with a relatively high proportion of acidic impurities.

The previously disclosed catalysts, including those described in the aforementioned patent and application, produce linear polyesters. It is within the scope of the invention to employ a mixture of such a catalyst with one of formula II to produce a mixture of branched polyesters of this invention and linear polyesters. The proportions of the two types of catalysts may be varied to afford the desired degree of branching.

The preparation of the branched polyesters of this invention is illustrated by the following examples.

Examples 2-5

The macrocyclic oligomers employed were prepared by the reaction of 5 millimoles of ethylene glycol and 95 millimoles of 1,4-butanediol with 100 millimoles of terephthaloyl chloride, substantially as described in the aforementioned patents and applications. Solutions in methylene chloride of the macrocyclic oligomers were divided into two samples; Sample A was washed first with aqueous acid, then with aqueous base and finally with deionized water, and Sample B with aqueous acid and water only. The methylene chloride was then removed by vacuum stripping and the products were pre-dried for 15 minutes at 100° C. under vacuum and then heated to 190° C. for 15 minutes with magnetic stirring, to form melts.

The molten oligomer melts were returned to atmospheric pressure by addition of nitrogen, polymerization catalysts in the desired proportion were added by injection and the mixtures were maintained at 190° C. for 20 or 30 minutes. During polymerization the products crystallized. The yields and molecular weights of the polyesters obtained were determined by gel permeation chromatography relative to standard polystyrene. The results are given in the following table, in comparison with controls employing two catalysts not part of the invention. The catalysts are identified in Table VII as follows:

    ______________________________________                                         I: Formula II, R.sup.3 = octyl, Z = C.                                         II: Formula II, R.sup.2 = ethyl, R.sup.3 = octyl, Z has formula III.           III: Formula II, R.sup.2 = ethyl, R.sup.3 = n-butyl, Z has formula III.        IV: Dioctyltin bis(2-ethylhexoxide).                                           V: Tetra-2-ethylhexyl titanate.                                                Catalyst          Time,   %             Mw/                                    Example Identity Mole %   min.  yield Mw    Mn                                 ______________________________________                                         2B      I        0.5      30    100   227,000                                                                              3.73                               3A      II       0.5      30     98   517,600                                                                              6.76                               3B      II       0.5      20     96   162,600                                                                              2.90                               4A      III      0.25     30    100   227,000                                                                              2.93                               4B      III      0.25     30     71    99,600                                                                              2.10                               5A      III      0.5      30    100   384,000                                                                              6.84                               5B      III      0.5      30     98   117,600                                                                              3.04                               Control 1A                                                                             IV       0.5      30    100   115,300                                                                              2.07                               Control 1B                                                                             IV       0.5      30    100    76,600                                                                              1.93                               Control 2A                                                                             V        0.25     30    100    97,100                                                                              1.87                               Control 2B                                                                             V        0.25     30     58    49,200                                                                              1.94                               Control 3A                                                                             V        0.5      30    100    62,700                                                                              2.54                               Control 3B                                                                             V        0.5      30     86    45,800                                                                              2.20                               ______________________________________                                    

The results in the table show that the branched polymers of the invention have uniformly high weight average molecular weights, even when the relatively impure B oligomer samples were employed. By contrast, the controls when employed with B samples afforded polymers of relatively low molecular weight. The higher molecular weight dispersities (Mw/Mn) of the polymers formed by the method of this invention are believed to be the result of their highly branched structures. 

What is claimed is:
 1. A branched poly(alkylene dicarboxylate) having the formula ##STR6## wherein R¹ is an alkylene or mono-or polyoxyalkylene radical containing a straight chain of about 2-8 carbon atoms, R² is a C₁₋₄ primary alkyl radical, A is a m- or p-linked monocyclic aromatic or alicyclic radical, X is a linear or branched organic end group, y has an average value of at least about 10 and m is 0 or
 1. 2. A branched poly(alkylene dicarboxylate)according to claim 1 wherein R¹ is ethylene or tetramethylene and A is m- or p-phenylene.
 3. A branched poly(alkylene dicarboxylate)according to claim 2 wherein A is p-phenylene.
 4. A branched poly(alkylene dicarboxylate) according to claim 2 wherein m is
 0. 5. A branched poly(alkylene dicarboxylate) according to claim 2 wherein m is 1 and R² is methyl or ethyl.
 6. A branched poly(alkylene dicarboxylate)according to claim 5 wherein R¹ is tetramethylene. 